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Enantioselective Hydroalkenylation of Olefins with Enol Sulfonates Enabled by Dual Copper Hydride and Palladium Catalysis

Alexander W. Schuppe, James Levi Knippel, Gustavo M. Borrajo‐Calleja, Stephen L. Buchwald

2021Journal of the American Chemical Society39 citationsDOIOpen Access PDF

Abstract

The catalytic enantioselective synthesis of α-chiral olefins represents a valuable strategy for rapid generation of structural diversity in divergent syntheses of complex targets. Herein, we report a protocol for the dual CuH- and Pd-catalyzed asymmetric Markovnikov hydroalkenylation of vinyl arenes and the anti-Markovnikov hydroalkenylation of unactivated olefins, in which readily available enol triflates can be utilized as alkenyl coupling partners. This method allowed for the synthesis of diverse α-chiral olefins, including tri- and tetrasubstituted olefin products, which are challenging to prepare by existing approaches.

Topics & Concepts

Markovnikov's ruleChemistryEnantioselective synthesisEnolCatalysisOlefin fiberCombinatorial chemistryPalladiumOrganic chemistryHydrideRegioselectivityHydrogenCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and Catalysis